CN104609415A - Low-cost large-scale preparation method of graphene - Google Patents
Low-cost large-scale preparation method of graphene Download PDFInfo
- Publication number
- CN104609415A CN104609415A CN201510074174.7A CN201510074174A CN104609415A CN 104609415 A CN104609415 A CN 104609415A CN 201510074174 A CN201510074174 A CN 201510074174A CN 104609415 A CN104609415 A CN 104609415A
- Authority
- CN
- China
- Prior art keywords
- solution
- graphene
- organic anion
- ion
- low cost
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a low-cost large-scale preparation method of graphene, which comprises the following steps: inserting an organic anion used as a carbon source material to the interlayers of lamellar inorganic hydrotalcite to obtain organic anion intercalated hydrotalcite which is used as a precursor; under the thermal-insulation action of the domain limit space of the hydrotalcite lamellae, calcining the organic anion intercalated hydrotalcite at lower temperature in an inert gas protective atmosphere to decompose, carbonize and graphitize the interlayer organic anion and enable the hydrotalcite lamellae to collapse, thereby forming metal oxides; after removing the metal oxides by acid washing, filtering, and carrying out ultrasonic dispersion in a hexanol solution to obtain a graphene dispersion solution; and carrying out freeze-drying on the dispersion solution to obtain the highly fluffy graphene powder. The method has the advantages of low cost and mild preparation conditions, and can implement pollution-free high-efficiency large-scale production of graphene under the condition of ensuring purity.
Description
Technical field
The invention belongs to new material technology field, being specifically related to a kind of low cost mass-producing can prepare the method for Graphene.
Technical background
Graphene (graphene), as a kind of novel two-dimension nano materials, is the Two Dimensional Free state atomic crystal of the unique existence found at present.It is by sp
2the carbon six-ring arrangement of hydbridized carbon atoms composition is formed, there is two-dimensional and periodic honeycomb lattice structure, it is nano material thin but the hardest in the world at present, there is excellent conduction, heat conductivility, make it have broad application prospects in fields such as solar cell, transparency electrode, ultracapacitor and stored materials.Mass-producing prepares high-quality graphene material for carrying out the research of Graphene intrinsic physico-chemical property Study and appliance, all has important science and technology and is worth.At present, prepare the method for Graphene still based on oxidation reduction process, but the Graphene that this method obtains has larger textural defect, the oxy radical introduced significantly can reduce the optical, electrical performance of Graphene, make it apply to be limited to, and this legal system is relatively large for difficulty, efficiency is low, and pollutes the environment.Therefore, be necessary to provide that a kind of low cost, environmental pollution are little, the preparation method of the Graphene that is easy to large-scale production.
The mineral compound with layered crystal structure that hydrotalcite (Layered double hydroxides) is made up of divalence and trivalent metal ion, composition general formula is: [M (II)
1-xm (III)
x(OH)
2]
x+(A
n x/n)
.mH
2o, wherein, M (II) and M (III) is respectively divalence and trivalent metal ion, and the interlayer anion of A to be valence mumber be-n, x is the mole number of M (III), and m is hydration water number.The layer structure of hydrotalcite to be interconnected by common edge by metallic hydrogen oxygen octahedra to form, and positively charged, layer superposes pushing up with layer, and interlayer is with hydrogen bond association, and interlayer has tradable negatively charged ion as counterion, makes total be electric neutrality.Hydrotalcite flaggy metal ion can modulation, and interlayer anion has intercalation assembleability, and can regulate and control assembling as required, thus hydrotalcite material is of a great variety, is used widely in catalysis, absorption, medicine etc.
Greying utilizes thermal activation to make the carbon atom of thermodynamic instability by the transform in order of turbostratic to crystal structure of graphite, in graphitizing process, use high-temperature heat treatment (more than 2000 DEG C) to provide energy to atomic rearrangement and structural transformation, therefore condition is harsh, cost is high.
Summary of the invention
The object of the present invention is to provide a kind of low cost mass-producing can prepare the method for Graphene.
Low cost mass-producing can prepare the method for Graphene, comprises the steps: to take organic anion as carbon source material, layered inorganic hydrotalcite layers is inserted in this organic anion, obtain organic anion intercalated houghite; Utilize the insulation effect of the confinement space between hydrotalcite flaggy, under the protection of lesser temps and rare gas element, calcine this organic anion intercalated houghite, the organic anion of interlayer is decomposed, then carbonize, greying, simultaneously, hydrotalcite flaggy subsides, and forms metal oxide; Then, after pickling removing metal oxide, filter and through ultrasonic disperse in ethanolic soln, obtain graphene dispersing solution; Dispersion liquid obtains the graphene powder of high loft again through lyophilize.
For the technical scheme realizing object of the present invention employing is as follows:
(1) chlorate of divalent metal or nitrate aqueous solution A, the chlorate of trivalent metal cation or nitrate aqueous solution B is prepared respectively;
(2) get organic anion to be well-dispersed in solvent D, obtain solution C;
(3) under ceaselessly violent stirring solution C condition, water solution A and aqueous solution B are dropwise added in solution C simultaneously;
(4) be added dropwise to complete rear mass ratio be 30% NaOH solution adjust ph be 6.0 ~ 12.0 obtain samples; Sample to be placed under 50 ~ 90 DEG C of conditions ageing 10 ~ 18 hours;
(5) by the sample deionized water wash of ageing to whole filtrate pH=7 ~ 8, filter, by the vacuum-drying 3 ~ 8 hours in 50 ~ 100 DEG C of temperature ranges of the filter cake that obtains, obtain organic anion intercalated houghite;
(6) organic anion intercalated houghite is placed in tube furnace, calcines under the protection of rare gas element, be warming up between 600 ~ 1600 DEG C, then calcining at constant temperature 1 ~ 6 hour, then cooling down is to room temperature, obtains crude product;
(7) by backflow in the acid solution of the crude product of gained at 60 ~ 200 DEG C 3 ~ 12 hours, with metal reagent inspection, no longer containing the divalence in intercalated houghite presoma and trivalent metal ion to phegma, then with deionized water wash for several times, filter; And through ultrasonic disperse 1-3h in ethanolic soln, obtain graphene dispersing solution, through lyophilize process after 1 day, obtain the graphene powder of high loft;
In water solution A of the present invention, divalent metal refers to Mg
2+, Zn
2+, Ni
2+, Co
2+, Mn
2+or Cu
2+in one;
In aqueous solution B of the present invention, trivalent metal cation refers to Al
3+, Cr
3+, Fe
3+, Co
3+, V
3+or Sc
3+in one;
Solvent D of the present invention, refers to the one in distilled water, acetone, ethyl acetate, ethanol, toluene or chloroform;
Organic anion of the present invention, refers to succinic ion, hexanodioic acid radical ion, sebacic acid radical ion, stearate radical ion, benzoate anion ion, dodecyl sulphate radical ion, the one in Witco 1298 Soft Acid ion or abietate ion;
After step (3), in solution C of the present invention, the mol ratio between divalent metal, trivalent metal cation, organic anion is 0.8 ~ 4.3:1:0.5 ~ 5.2
Rare gas element of the present invention refers to the one in nitrogen, argon gas or helium;
Calcining of the present invention, its objective is that the organic anion making interlayer is decomposed, then carbonizes, greying;
Hydrotalcite flaggy of the present invention is made up of octahedra to be interconnected by common edge of the hydrogen-oxygen of the divalence in solution A, B, trivalent metal;
Hydrotalcite flaggy of the present invention subsides, and forms metal oxide and refers to that the metallic hydrogen oxygen octahedra at high temperature forming hydrotalcite flaggy decomposes, produce metal oxide;
Acid solution of the present invention, refers to the one in hydrochloric acid (massfraction is: 20%-37%), nitric acid (massfraction is: 50%-70%) or sulfuric acid (massfraction is: 50%-80%);
Whether metal reagent of the present invention selects according to the divalence in intercalated houghite presoma and trivalent metal ion, exist for checking these metal ions in phegma;
The aqueous ethanolic solution of ethanolic soln of the present invention to be volume fraction be 10%-90%.
The present invention utilizes the insulation effect of confinement space between hydrotalcite flaggy, graphitizing process is temperature required low in free space to make the temperature required ratio of carbon source material graphitizing process, simultaneously, due to the compartmentation of hydrotalcite flaggy, make graphited carbon atom arrangement become individual layer or minority which floor, form Graphene.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of Graphene of the present invention;
Fig. 2 is the Raman spectrogram of Graphene of the present invention.
Embodiment
With nonlimiting examples, the present invention is more specifically described in detail below, will the understanding to the present invention and advantage thereof be contributed to, and not as a limitation of the invention, for the processing parameter do not indicated especially, can refer to routine techniques and carry out.
embodiment 1
(1) 0.28MZn (Cl) is prepared respectively
2aqueous solution 1L, 0.1M V (Cl)
3aqueous solution 1L be solution A and B;
(2) the pure rosin of superfine getting 0.08mol is scattered in 100ml dehydrated alcohol in advance, and this is solution C;
(3) under ceaselessly violent stirring solution C condition, water solution A and aqueous solution B are dropwise added in solution C simultaneously;
(4) be added dropwise to complete rear mass ratio be 30% NaOH solution adjust ph be 10.0 acquisition samples; Sample to be placed under 70 DEG C of conditions ageing 10 hours;
(5) by the sample deionized water wash of ageing to whole filtrate pH=8, filter, by the vacuum-drying 5 hours in 80 DEG C of temperature ranges of the filter cake that obtains, obtain abietate intercalated houghite;
(6) abietate intercalated houghite is placed in tube furnace, calcines under the protection of argon gas, be warming up between 800 DEG C, then calcining at constant temperature 6 hours, then cooling down is to room temperature, obtains crude product;
(7) by the hydrochloric acid soln of the crude product of gained at 90 DEG C, (massfraction is: backflow 4 hours 30%), uses zinc, vanadium ion reagent test respectively, no longer containing zinc, vanadium ion to phegma, then with deionized water wash several, filters; And at ethanolic soln, (massfraction is: through ultrasonic disperse 2h 50%), obtain graphene dispersing solution, through lyophilize process after 1 day, obtains the graphene powder of high loft.
embodiment 2
(1) 0.2M Mg (NO is prepared respectively
3)
2aqueous solution 1L, 0.05M Fe (NO
3)
3aqueous solution 1L be solution A and B;
(2) Soduxin getting 0.032mol is scattered in 100ml distilled water in advance, and this is solution C;
(3) under ceaselessly violent stirring solution C condition, water solution A and aqueous solution B are dropwise added in solution C simultaneously;
(4) be added dropwise to complete rear mass ratio be 30% NaOH solution adjust ph be 10.0 acquisition samples; Sample to be placed under 60 DEG C of conditions ageing 14 hours;
(5) by the sample deionized water wash of ageing to whole filtrate pH=7, filter, by the vacuum-drying 5 hours in 60 DEG C of temperature ranges of the filter cake that obtains, obtain succinic intercalated houghite;
(6) succinic intercalated houghite is placed in tube furnace, calcines under the protection of helium, be warming up between 900 DEG C, then calcining at constant temperature 4 hours, then cooling down is to room temperature, obtains crude product;
(7) by the sulphuric acid soln 60 DEG C at of the crude product of gained at 90 DEG C (massfraction is: backflow 2 hours 50%), respectively with magnesium, iron ion agent inspection, no longer containing magnesium, iron ion to phegma, then with deionized water wash for several times, filter; And at ethanolic soln, (massfraction is: through ultrasonic disperse 2h 80%), obtain graphene dispersing solution, through lyophilize process after 1 day, obtains the graphene powder of high loft.
embodiment 3
(1) 0.3M Ni (Cl) is prepared respectively
2aqueous solution 1L, 0.15M Al (Cl)
3aqueous solution 1L be solution A and B;
(2) sodium stearate of getting 0.12mol is scattered in 100ml distilled water in advance, and this is solution C;
(3) under ceaselessly violent stirring solution C condition, water solution A and aqueous solution B are dropwise added in solution C simultaneously;
(4) be added dropwise to complete rear mass ratio be 30% NaOH solution adjust ph be 9.0 acquisition samples; Sample to be placed under 90 DEG C of conditions ageing 8 hours;
(5) by the sample deionized water wash of ageing to whole filtrate pH=7, filter, by the vacuum-drying 3 hours in 100 DEG C of temperature ranges of the filter cake that obtains, obtain stearate radical intercalated hydrotalcite;
(6) stearate radical intercalated hydrotalcite is placed in tube furnace, calcines under the protection of nitrogen, be warming up between 1200 DEG C, then calcining at constant temperature 1 hour, then cooling down is to room temperature, obtains crude product;
(7) by the nitric acid of the crude product of gained at 80 DEG C, (massfraction is: backflow 10 hours 60%), uses nickel, aluminum ion reagent test respectively, no longer containing nickel, aluminum ion to phegma, then with deionized water wash several, filters; And at ethanolic soln, (massfraction is: through ultrasonic disperse 2h 80%), obtain graphene dispersing solution, through lyophilize process after 1 day, obtains the graphene powder of high loft.
Claims (9)
1. low cost mass-producing can prepare the preparation method of Graphene, it is characterized in that:
(1) chlorate of divalent metal or nitrate aqueous solution A, the chlorate of trivalent metal cation or nitrate aqueous solution B is prepared respectively;
(2) getting organic anion is well-dispersed in solvent D, and this is solution C;
(3) under ceaselessly violent stirring solution C condition, water solution A and aqueous solution B are dropwise added in solution C simultaneously;
(4) be added dropwise to complete rear mass ratio be 30% NaOH solution adjust ph be 6.0 ~ 12.0 obtain samples; Sample to be placed under 50 ~ 90 DEG C of conditions ageing 10 ~ 18 hours;
(5) by the sample deionized water wash of ageing to whole filtrate pH=7 ~ 8, filter, by the vacuum-drying 3 ~ 8 hours in 50 ~ 100 DEG C of temperature ranges of the filter cake that obtains, obtain organic anion intercalated houghite;
(6) organic anion intercalated houghite is placed in tube furnace, calcines under the protection of rare gas element, be warming up between 600 ~ 1600 DEG C, then calcining at constant temperature 1 ~ 6 hour, then cooling down is to room temperature, obtains crude product;
(7) by backflow in the acid solution of the crude product of gained at 60 ~ 200 DEG C 3 ~ 12 hours, with metal reagent inspection, no longer containing the divalence in intercalated houghite presoma and trivalent metal ion to phegma, then with deionized water wash for several times, filter; And through ultrasonic disperse 1-3h in ethanolic soln, obtain graphene dispersing solution, through lyophilize process after 1 day, obtain the graphene powder of high loft.
2. a kind of low cost according to claim 1 mass-producing can prepare preparation method; it is characterized in that; described organic anion refers to succinic ion; hexanodioic acid radical ion; sebacic acid radical ion, stearate radical ion, benzoate anion ion; dodecyl sulphate radical ion, the one in Witco 1298 Soft Acid ion or abietate ion.
3. preparation method according to claim 1, is characterized in that rare gas element refers to the one in nitrogen, argon gas or helium.
4. a kind of low cost according to claim 1 can large-scale preparation method; it is characterized in that after step (3); in solution C of the present invention, the mol ratio between divalent metal, trivalent metal cation, organic anion is 0.8 ~ 4.3:1:0.5 ~ 5.2.
5. a kind of low cost according to claim 1 can large-scale preparation method, it is characterized in that described trivalent metal cation refers to Al
3+, Cr
3+, Fe
3+, Co
3+, V
3+or Sc
3+in one.
6. a kind of low cost according to claim 1 can large-scale preparation method, it is characterized in that described divalent metal refers to Mg
2+, Zn
2+, Ni
2+, Co
2+, Mn
2+or Cu
2+in one.
7. a kind of low cost according to claim 1 can large-scale preparation method, it is characterized in that described solvent D refers to the one in distilled water, acetone, ethyl acetate, ethanol, toluene or chloroform.
8. a kind of low cost according to claim 1 can large-scale preparation method, it is characterized in that described acid solution, refers to that massfraction is the hydrochloric acid of 20%-37%, the massfraction one that to be 50%-70% nitric acid or massfraction be in 50%-80% sulfuric acid.
9. a kind of low cost according to claim 1 can large-scale preparation method, it is characterized in that described ethanolic soln to be volume fraction be the aqueous ethanolic solution of 10%-90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510074174.7A CN104609415B (en) | 2015-02-12 | 2015-02-12 | A kind of low cost can the scale method of preparing Graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510074174.7A CN104609415B (en) | 2015-02-12 | 2015-02-12 | A kind of low cost can the scale method of preparing Graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104609415A true CN104609415A (en) | 2015-05-13 |
| CN104609415B CN104609415B (en) | 2016-07-06 |
Family
ID=53144116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510074174.7A Expired - Fee Related CN104609415B (en) | 2015-02-12 | 2015-02-12 | A kind of low cost can the scale method of preparing Graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104609415B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776181A (en) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | Preparation method of flaky nanoholes carbon and carbon nanotube composite |
| CN107311166A (en) * | 2017-05-18 | 2017-11-03 | 北京化工大学 | A kind of preparation method and its usage of thin layer carbon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| US20120202056A1 (en) * | 2009-10-15 | 2012-08-09 | Bayer Technology Services | Composite materials having graphene layers and production and use thereof |
| CN102910622A (en) * | 2012-10-25 | 2013-02-06 | 常州大学 | Preparation method of two-dimensional nano-graphene |
-
2015
- 2015-02-12 CN CN201510074174.7A patent/CN104609415B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120202056A1 (en) * | 2009-10-15 | 2012-08-09 | Bayer Technology Services | Composite materials having graphene layers and production and use thereof |
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| CN102910622A (en) * | 2012-10-25 | 2013-02-06 | 常州大学 | Preparation method of two-dimensional nano-graphene |
Non-Patent Citations (1)
| Title |
|---|
| XIAOYA YUAN,ET AL.: "Calcined graphene MgAl-layered double hydroxides for enhanced Cr(VI) removal", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776181A (en) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | Preparation method of flaky nanoholes carbon and carbon nanotube composite |
| CN105776181B (en) * | 2016-04-29 | 2018-12-21 | 大连理工大学 | A kind of preparation method of flake nano porous carbon and carbon nano tube compound material |
| CN107311166A (en) * | 2017-05-18 | 2017-11-03 | 北京化工大学 | A kind of preparation method and its usage of thin layer carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104609415B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gou et al. | Flower-like nickel-cobalt hydroxides converted from phosphites for high rate performance hybrid supercapacitor electrode materials | |
| Hu et al. | Effect of Cu (I)–N active sites on the N2 photofixation ability over flowerlike copper-doped g-C3N4 prepared via a novel molten salt-assisted microwave process: the experimental and density functional theory simulation analysis | |
| Lan et al. | Hydrothermal synthesis of γ-MnOOH nanorods and their conversion to MnO2, Mn2O3, and Mn3O4 nanorods | |
| CN102910622B (en) | Preparation method of two-dimensional nano-graphene | |
| Ming et al. | Microwave–hydrothermal synthesis of birnessite-type MnO2 nanospheres as supercapacitor electrode materials | |
| CN103657639B (en) | Preparation method and silicon modification method of visible light catalysis material for graphene/bismuth tungstate flake nanostructure | |
| CN102716734B (en) | Preparation method for cerium oxide/graphene oxide nanocomposite | |
| CN103303912A (en) | Preparation method of high-specific-surface-area porous nitrogen-doped graphitizing carbon nanomaterial | |
| CN102583347B (en) | Method for preparing graphene by using interlaminar two-dimensional confinement space of inorganic laminar material | |
| CN106587017A (en) | Porous graphene and preparation method thereof | |
| Yuan et al. | Vacuum topotactic conversion route to mesoporous orthorhombic MoO3 nanowire bundles with enhanced electrochemical performance | |
| CN103700829B (en) | Titanium dioxide (B)-Graphene is from the preparation method of winding nano composite material | |
| Salkar et al. | Designing a 3D nanoporous network via self-assembly of WO 3 nanorods for improved electrocapacitive performance | |
| CN104511293A (en) | Bismuth oxychloride-iron bismuth titanate composite photocatalyst and preparation method thereof | |
| Zhao et al. | Constructing high-performance N-doped carbon nanotubes anode by tuning interlayer spacing and the compatibility mechanism with ether electrolyte for sodium-ion batteries | |
| Cao et al. | Three-dimensional porous iron vanadate nanowire arrays as a high-performance lithium-ion battery | |
| Chatterjee et al. | Enhanced electrochemical properties of Co3O4 with morphological hierarchy for energy storage application: a comparative study with different electrolytes | |
| CN102718209B (en) | Method for preparing graphene based on reduction of divalent iron ion | |
| Wang et al. | Research on Li3V2 (PO4) 3/Li4Ti5O12/C composite cathode material for lithium ion batteries | |
| CN108452813A (en) | A kind of MoS2/SrFe12O19The preparation method of composite magnetic photochemical catalyst | |
| CN103420419A (en) | High-temperature hydrothermal mixing synthesis method for vanadium dioxide powder | |
| CN104609414B (en) | A kind of preparation method of three-dimensional porous graphene composite material | |
| CN104609415A (en) | Low-cost large-scale preparation method of graphene | |
| Wang et al. | Insight into defect-engineered gallium oxynitride nanoparticle-based electrodes with improved electrochemical performance for supercapacitors | |
| Wei et al. | High rate performances of hydrogen titanate nanowires electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160706 Termination date: 20220212 |